Surface modified polymeric materials, modified functionalized polymers, functional polymers, and methods

ABSTRACT

The present invention relates to new, improved or modified polymer materials, membranes, substrates, and the like and to new, improved or modified methods for permanently modifying the physical and/or chemical nature of surfaces of the polymer materials, membranes, or substrates for a variety of end uses or applications. For example, one improved method uses a carbene and/or nitrene modifier to chemically modify a functionalized polymer to form a chemical species which can chemically react with the surface of a polymer substrate and alter its chemical reactivity. Furthermore, this invention can be used to produce chemically modified membranes, fibers, hollow fibers, textiles, and the like.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority to and the benefit of each ofU.S. provisional patent application Ser. No. 61/508,725 filed Jul. 18,2011, and U.S. provisional patent application Ser. No. 61/547,812 filedOct. 17, 2011, both of which are hereby fully incorporated by referenceherein.

FIELD OF THE INVENTION

The instant invention is directed to surface modified polymericmaterials, modified functionalized polymers, functional polymers,chemically modified substrates including modified functionalizedpolymers, methods of making and/or using surface modified polymericmaterials, modified functionalized polymers, functional polymers, and/orchemically modified substrates including modified functionalizedpolymers, methods of modifying a functionalized polymer and/or methodsof using modified functionalized polymers to chemically react with thesurface of a substrate, and/or methods of using such chemically modifiedsubstrates. At least certain embodiments are directed to modifiedfunctionalized polymers, functional polymers, and methods of modifyingfunctionalized polymers for chemically modifying porous and/or nonporouspolymer substrates and/or methods of using such modified substrates. Atleast selected embodiments are directed to modified functionalizedpolymers, functional polymers, and methods of modifying functionalizedpolymers for chemically modifying porous and/or microporous polymersubstrates and methods of using such modified substrates. At leastcertain embodiments are directed to modifying certain functionalizedpolymers to enable them to effect a change in the surface property of asubstrate. In accordance with at least selected possibly preferredembodiments, the invention is directed to using a carbene and/or nitrenecrosslinking modifier to chemically modify a functionalized polymer toform a modified functionalized polymer which can chemically modify thesurface of a substrate and effect a change in the surface properties ofthe substrate for an intended application. In accordance with at leastselected possibly preferred embodiments, the invention is directed tousing a carbene and/or nitrene crosslinking modifier (component B) tocovalently modify a polymeric surface with a functionalized polymer(component A). Such a modification may alter the chemical reactivity ofthe polymeric surface enabling the modified substrate to have aspecifically designed functionality for an intended end use orapplication.

BACKGROUND OF THE INVENTION

Various methods exist to modify the physical or chemical nature ofsurfaces of polymeric materials. Certain known modifications of surfacesof polymeric materials are often fugitive and fail to permanently modifythe polymer substrate for a variety of end use applications.

One such known method is a treatment or pre-treatment of the surface ofthe polymer substrate, for example using ultraviolet light, plasma, orcorona treatment. Such treatments may be harsh, particularly for thinfilms and certain polymer classes. Using these methodologies may cause arisk of mechanical or chemical damage to the surface of the polymersubstrate. Damage, in some cases, can compromise the performance of themodified polymer substrate for its intended end use application.

Thus there exists a need for improved methods to modify the physicaland/or chemical nature of surfaces of polymeric materials. Inparticular, a need exists for improved or novel methods for permanentlymodifying a polymer substrate for a variety of end use applications,surface modified polymeric materials, modified functionalized polymers,functional polymers, uses of such materials, and the like.

SUMMARY OF THE INVENTION

In accordance with at least selected embodiments, the present inventionmay provide or at least address the need for improved methods to modifythe physical and/or chemical nature of surfaces of polymeric materials,for improved or novel methods for permanently modifying the polymersubstrate for a variety of end use applications, for surface modifiedpolymeric materials, for modified functionalized polymers, forfunctional polymers, uses of such materials, and the like.

At least certain embodiments of the present invention may address theabove needs and are directed to modified functionalized polymers,functional polymers and chemically modified substrates includingmodified functionalized polymers, methods of modifying a functionalizedpolymer and/or methods of using modified functionalized polymers tochemically react with the surface of a substrate, and/or methods ofusing such chemically modified substrates.

More particularly, at least certain embodiments are directed tomodifying certain functionalized polymers to enable them to effect achange in the surface property of a substrate. In accordance with atleast selected preferred embodiments, the invention is directed to usingpreferably a carbine, nitrene or combined carbine and nitrenecrosslinking modifier (component B or modifier component B) or precursorthereof, to chemically modify a functionalized polymer (component A orfunctionalized component A) to form a modified functionalized polymerA-B which can then chemically modify the surface of a polymer substrateand effect a change in the surface properties of the polymer substratefor an intended application, product, process, or end use. A carbene(R—C:) is any member of a class of highly reactive molecules containingdivalent carbon atoms, that is, carbon atoms that utilize only two ofthe four bonds they are capable of forming with other atoms with noassociated ionic charge. A nitrene (R—N:) is the nitrogen analogue of acarbene and has only six valence electrons. Nitrenes and carbenes arereactive intermediates that can be reacted with a functional component Ato form a special chemical species referred to herein as a ‘modifiedfunctionalized polymer A-B’ which is capable of reacting with a polymersubstrate resulting in the attachment of a specific chemicalfunctionality to the polymer substrate and tailoring the chemicalstructure or properties of the polymer substrate specifically for anintended end use.

The chemical reaction of a modified functionalized polymer A-B that hasa specific chemical functionality with the polymeric surface of thesubstrate would result in a permanent modification (chemicalmodification) of the polymeric surface of the substrate. Morespecifically, reacting functionalized component A with modifiercomponent B can generate a modified functionalized polymer A-B which iscapable of acting as an adhesion promoter/demoter agent.

The chemical reaction of a modified functionalized polymer A-B that hasa specific chemical functionality with the polymeric surface of thesubstrate would result in a permanent modification of the polymericsurface of the substrate. More specifically, reacting functionalizedcomponent A with modifier component B can generate a modifiedfunctionalized polymer A-B which is capable of acting as an adhesionpromoter/demoter agent which then can chemically bond to the surface ofthe polymer substrate and change the surface energy of the polymersubstrate leading to enhanced adhesion properties in adhesive orlamination applications.

Still more specifically, the modified functionalized polymer A-B cancovalently modify a polymer substrate which has a lower or highersurface energy that counteracts the direct attachment of functionalcomponent A. More specifically, modified functionalized polymer A-B canmodify the polymer substrate which has a polarity that limits and/orprevents the direct attachment of functional polymer A. Morespecifically, the modified functionalized polymer A-B can modify thepolymer substrate which has a surface that is hydrophilic or hydrophobicwhich can limit and/or prevent the direct attachment of functionalcomponent A. Still more specifically, modified functionalized polymerA-B can modify the polymer substrate which has a surface that isoleophilic or oleophobic which can limit and/or prevent the attachmentof functional component A.

Yet more specifically, the modified functionalized polymer A-B canmodify a polymer substrate by changing its surface energy. Morespecifically, the modified functionalized polymer A-B can be used toincrease or decrease the effective surface energy of the polymersubstrate to improve its compatibility with, for example, coatings,materials, adjoining layers, or the like.

More specifically, modified functionalized polymer A-B can modify thepolymer substrate which has a polarity that limits and/or prevents thedirect attachment of functional polymer A, can modify the polymersubstrate which has a surface that is hydrophilic or hydrophobic whichcan limit and/or prevent the direct attachment of functional componentA, or can modify the polymer substrate which has a surface that isoleophilic or oleophobic which can limit and/or prevent the attachmentof functional component A.

At least certain selected embodiments of the present invention addressthe above described needs and are directed to modified functionalizedpolymers, functional polymers and chemically modified substratesincluding modified functionalized polymers, methods of modifying afunctionalized polymer and/or methods of using modified functionalizedpolymers to chemically react with the surface of a substrate, and/ormethods of using such chemically modified substrates. At least certainembodiments are directed to modified functionalized polymers, functionalpolymers, and methods of modifying functionalized polymers forchemically modifying porous and nonporous polymer substrates and methodsof using such modified substrates. At least selected embodiments aredirected to modified functionalized polymers, functional polymers, andmethods of modifying functionalized polymers for chemically modifyingporous and microporous polymer substrates and methods of using suchmodified substrates.

At least certain selected embodiments of the present invention addressthe need to modify the surface of porous polymeric substrates. At leastselected embodiments of the present invention address the above needand/or are directed to modified porous polymeric membrane substrates,methods of making modified polymeric porous membrane substrates, and/ormethods of using modified polymeric porous membrane substrates,chemically modified polyolefin microporous membranes, methods of makingchemically modified polyolefin microporous membranes, and/or methods ofusing chemically modified polyolefin microporous membranes, chemicallymodified polyolefin microporous battery separators or battery separatormembranes, methods of making chemically modified polyolefin microporousbattery separators or battery separator membranes, and/or methods ofusing chemically modified polyolefin microporous battery separators orbattery separator membranes, chemical modification of polyolefinmicroporous battery separators or separator membranes by the reaction ofthe modified functionalized polymer A-B which contains the carbeneand/or nitrene intermediate with the carbon-hydrogen bonds of thepolyolefin to form carbon-carbon or covalent bonds with the polyolefin,methods of improving the hydrophilicity or wettability of the polyolefinmicroporous battery separators or separator membranes in lithium-ionrechargeable batteries, and/or methods of introducing crosslinking intothe polyolefin microporous battery separators or separator membranes,and/or the like.

In accordance with at least selected possibly preferred embodiments ofthe invention, chemical modification of at least a portion of thesurface of polyolefin microporous separators or membranes can beaccomplished by the functionalized polymer A containing the carbeneand/or nitrene intermediate with, for example, the carbon-hydrogen bondsof the polyolefin. This chemical reaction or treatment based onfunctionalized polymer A (component A or functionalized component A)containing the carbene and/or nitrene intermediate provides a method ofmore permanently improving the wettability of polyolefin microporousseparators in lithium-ion rechargeable batteries. In addition, thepreferred reaction of functionalized polymer A containing the carbeneand/or nitrene intermediate with the C—C and C—H bonds in at least asurface layer of polyolefin microporous separator membranes can be usedto introduce a crosslinking functionality into the polyolefin which canbe used to improve the high temperature stability of the polyolefinmicroporous separators or membranes.

In accordance with at least certain selected embodiments, the presentinvention addresses the need to modify the surface of porous polymericsubstrates. At least selected embodiments of the present inventionaddress the above need and are directed to modified porous polymericmembrane substrates, methods of making modified polymeric porousmembrane substrates, and methods of using modified polymeric porousmembrane substrates. More particularly, the invention is directed tochemically modified polyolefin microporous membranes, methods of makingchemically modified polyolefin microporous membranes, and methods ofusing chemically modified polyolefin microporous membranes. Still moreparticularly, the invention is directed to chemically modifiedpolyolefin microporous waterproof/breathable textile membranes, methodsof making chemically modified polyolefin microporouswaterproof/breathable textile membranes, and methods of using chemicallymodified polyolefin microporous waterproof/breathable textile membranes.In accordance with at least selected preferred embodiments, theinvention is directed to chemical modification of polyolefin microporouswaterproof/breathable textile membranes by the reaction of the modifiedfunctionalized polymer A-B which contains the carbene and/or nitreneintermediate with the carbon-hydrogen bonds of the polyolefin, methodsof decreasing the surface energy or imparting oleophobicity towaterproof/breathable textile membranes to improve the foulingresistance of waterproof/breathable textiles and/or improve thedurability of the membranes' waterproofness, and/or the like.

In accordance with at certain selected embodiments, the presentinvention addresses the need to modify the surface of polymeric textilefibers. At least selected embodiments of the present invention addressthe above need and are directed to modified polymeric textile fibers,methods of making modified polymeric textile fibers, and methods ofusing modified polymeric textile fibers. More particularly, theinvention is directed to chemically modified polyolefin textile fibers,methods of making chemically modified polyolefin textile fibers, andmethods of using chemically modified polyolefin textile fibers. Inaccordance with at least selected possibly preferred embodiments, theinvention is directed to chemical modification of polymeric textilefibers by the reaction of the modified functionalized polymer A-B whichcontains the carbene and/or nitrene intermediate with thecarbon-hydrogen bonds of the polymeric textile fibers, methods ofdecreasing the surface energy or imparting oleophobicity to polymerictextile fibers to improve the fouling resistance of polymeric textilefibers and/or improve the durability of the textile fibers'waterproofness, and/or the like.

At least certain objects, embodiments, aspects, and/or examples of theinstant invention are directed to surface modified polymeric materials,modified functionalized polymers, functional polymers, chemicallymodified substrates including modified functionalized polymers, methodsof making and/or using surface modified polymeric materials, modifiedfunctionalized polymers, functional polymers, and/or chemically modifiedsubstrates including modified functionalized polymers, methods ofmodifying a functionalized polymer and/or methods of using modifiedfunctionalized polymers to chemically react with the surface of asubstrate, and/or methods of using such chemically modified substrates.At least certain embodiments are directed to modified functionalizedpolymers, functional polymers, and methods of modifying functionalizedpolymers for chemically modifying porous and/or nonporous polymersubstrates and/or methods of using such modified substrates. At leastselected embodiments are directed to modified functionalized polymers,functional polymers, and methods of modifying functionalized polymersfor chemically modifying porous and/or microporous polymer substratesand methods of using such modified substrates. At least certainembodiments are directed to modifying certain functionalized polymers toenable them to effect a change in the surface property of a substrate.In accordance with at least selected possibly preferred embodiments, theinvention is directed to using a carbene and/or nitrene crosslinkingmodifier to chemically modify a functionalized polymer to form amodified functionalized polymer which can chemically modify the surfaceof a substrate and effect a change in the surface properties of thesubstrate for an intended application. In accordance with at leastselected possibly preferred embodiments, the invention is directed tousing a carbene and/or nitrene crosslinking modifier (component B) tocovalently modify a polymeric surface with a functionalized polymer(component A). Such a modification may alter the chemical reactivity ofthe polymeric surface enabling the modified substrate to have aspecifically designed functionality for an intended end use orapplication.

At least certain objects, embodiments, aspects, and/or examples of theinstant invention are directed to improved or novel methods forpermanently modifying a polymer substrate for a variety of end uses orapplications, surface modified polymeric materials, modifiedfunctionalized polymers, functional polymers, uses of such materials,and/or the like.

Other objects, embodiments, aspects, or examples of the presentinvention may be shown or described in the drawings, the detaileddescription or the claims.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a formulaic reaction illustration of nitrene generation,carbine generation, and the insertion mechanism or reaction inaccordance with at least selected possibly preferred embodiments of thepresent invention. For example, FIG. 1 illustrates the chemicalreactions showing R/R′ groups modified to tailor surface characteristicsof a polyolefin, such as the surface of a polyolefin substrate, forexample, the R/R′ groups can be modified to tailor surfacecharacteristics such as wetting.

FIG. 2 is a schematic illustration of a surface modified polymericmaterial or a chemically modified substrate including modifiedfunctionalized polymers in accordance with at least selected possiblypreferred embodiments of the present invention.

FIG. 3 is a schematic illustration of a coated or treated surfacemodified polymeric material or a coated or treated chemically modifiedsubstrate, for example, modified by modified functionalized polymers tofacilitate the desired coating or treatment (such as by raising orlowering the surface energy of the polymeric material or substratesuface) in accordance with at least selected possibly preferredembodiments of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

At least certain embodiments of the present invention may address theabove needs and/or are directed to new, improved, or modified surfacemodified polymeric materials, modified functionalized polymers,functional polymers, and/or chemically modified substrates includingmodified functionalized polymers, and/or methods of modifying afunctionalized polymer and/or methods of using modified functionalizedpolymers to chemically react with the surface of a substrate, and/ormethods of using such chemically modified substrates.

More particularly, certain embodiments are directed to modifying certainfunctionalized polymers to enable them to effect a change in the surfaceproperty of a substrate. In accordance with at least selected preferredembodiments, the invention is preferably directed to using a carbeneand/or nitrene crosslinking modifier (component B or modifier componentB) to chemically modify a functionalized polymer (component A orfunctional or functionalized component A) to form a modifiedfunctionalized polymer A-B which can then chemically modify the surfaceof a polymer substrate and effect a change in the the surface propertiesof the polymer substrate for an intended application.

A carbene (R—C:) is any member of a class of highly reactive moleculescontaining divalent carbon atoms, that is, carbon atoms that utilizeonly two of the four bonds they are capable of forming with other atoms.A nitrene (R—N:) is the nitrogen analogue of a carbene and has only 6valence electrons. Nitrenes and carbenes are reactive intermediates thatmay have unique reactivity towards both functional and nominallynonfunctional substrates. Although there may be methods available tomodify certain functional polymeric substrates, the current inventionprovides a method well suited to modify those polymeric substrates thatare nonfunctional, that is, they do not contain functional groups. Mostpolyolefins are essentially “nonfunctional” as they do not readilyaccept modification without significant consequences to the mechanicalor chemical stability of the material. Carbene and/or nitrene basedintermediates provide an opportunity to modify nonfunctional polyolefinswithout the severe degradation that typically occurs with manyconventional surface modification approaches. Furthermore, the use ofcarbene, nitrene or combined carbene and nitrene based intermediates ofthe present invention may provide opportunities that can be applied tomost, if not all polymeric substrates without regard for chemicalmodification that is specific to a functional group. The reactivecarbene and/or nitrene based intermediates of the present invention havethe advantage of being capable of inserting themselves intocarbon-hydrogen chemical bonds of a polyolefin polymeric substrate. Thespecial chemical reactivity of carbene and/or nitrene basedintermediates allows functional component A-B to react with“nonfunctional” materials providing a means to attach component A to thepolymer substrate.

In accordance with one example of the present invention, modifiercomponent B with a plurality of carbene and/or nitrene intermediates orprecursors can be mixed with one or more desired functional componentA's to form a special chemical species referred to herein as a ‘multiplereactive site modified functionalized polymer A-B’. Given theappropriate ratio and formulation conditions, this coacervate is capableof further reacting with a given polymer substrate that could bepolyolefinic in nature, or some other synthetic or naturally derivedpolymer material resulting in the attachment of a specific, desiredchemical functionality to the polymer substrate that tailors thechemical structure of the polymer substrate specifically for an intendedend use.

The chemical reaction of a modified functionalized polymer A-B that hasa specific chemical functionality with the polymeric surface of thesubstrate may result in a permanent, covalent modification of a desiredpolymeric surface with the chemical functionality of component A. Inaccordance with the present invention, one example is a polyolefinicsubstrate modified with a poly(ethylene oxide) polymer or oligomer(example component A). A component B having a plurality of carbeneand/or nitrene generating species can act as a tether between apolyolefin surface and a poly(ethylene oxide) component A. The resultingcomposite material (polyolefin substrate with functionalized componentA-B) has bulk properties resembling the polyolefin substrate, but withthe surface properties of poly(ethylene oxide). For instance, the postmodified polyolefin surface may appear to have a much higher surfaceenergy than normal polyolefin, approaching that of a typicalpoly(ethylene oxide) substrate surface, depending on the quality andextent of modification. Applications for such functionalized componentA-B modified polymeric substrates of the present invention include forexample, enhanced wettability of battery separator materials,anti-fouling, and adhesion promotion for certain coatings, materials,layers, or treatments among others.

Other polymeric materials that could be used as a component A in thefunctionalized component A-B modified polymeric substrate may preferablyinclude materials with different surface properties than the basesubstrate. For example, a particular antifouling application may requirea fluorinated functional component A. Utilizing fluorinated polymers oroligomers as functional component A, polymer substrate surfaces can beobtained that have properties similar to fluorinated materials withrespect to hydrophobic or oleophobic behavior that do not suffer thesame bulk mechanical disadvantages as the bulk fluorinated materials.

In accordance with one example of the present invention, this conceptcan be extended to other substrates such as polyamide substratescommonly used for carpeting or textile applications. Certain knownfinishes for polyamide substrates typically have very little chemicalfunctionality to facilitate attachment. Other typical covalentmodifications could prove detrimental to the bulk properties of thematerial and lead to degraded end use properties of the polyamidesubstrate. The carbine and/or nitrene tether concept of the presentinvention can add standard textile finishes to these types of polyamidesubstrates.

In accordance with at least selected embodiments of the presentinvention, microporous polyolefin membrane substrates can be modifiedwith selected functionalized components A-B to exclude various materialssuch as alcohols, aliphatics and aromatic compounds. Microporouspolyolefin membranes tend to absorb significant amounts of oil withintheir pores. The present functionalized component A-B treatment ormodification can be used to modify the surface of microporous polyolefinmembranes to exclude materials such as alcohols, aliphatics or aromaticcompounds, thereby creating modified substrates for use in new types ofseparations.

In accordance with at least selected embodiments of the presentinvention, applications also exist to lower the surface energy ofmicroporous polyolefin membranes using a functionalized component A-B.The comfort of waterproof outerwear can be greatly improved by makingthe garment more breathable to enable the body moisture of the wearer toevaporate through the fabric of the waterproof outerwear. Thisfunctionality is commonly referred to as “waterproof/breathable”outerwear. Many waterproof/breathable garments incorporate non-porousmaterials that rely on molecular transport of water molecules to achievebreathability. There is a need to provide improved breathability byincorporating truly porous membranes that allow water vapor molecules toevaporate through diffusion in air, thus greatly increasingbreathability and enhancing wearer comfort. One disadvantage of certainmicroporous membranes is they can become fouled by natural body oils orother oils resulting in a reduction in the waterproof performance of themembrane. This disadvantage can be overcome using the present inventionto modify the surface of the microporous membrane, for example, with afluorinated compound, to make the membrane surface oleophobic andresistant to fouling by natural body oils or other oils.

In accordance with at least selected embodiments of the presentinvention, applications also exist to lower the surface energy ofpolymeric textile fibers and/or fabrics using a functionalized componentA-B. The waterproof performance and/or stain resistance of polymerictextile fibers and fabrics is often achieved through the application ofdurable water repellent (“DWR”) coatings and finishes. These DWRcoatings and finishes have poor durability and wear off due to repeatedwashing and/or use. Some textile fibers and/or fabrics, for examplethose made of acrylic, are less readily treated with DWR coatings andoften are not used in applications where water and/or stain resistanceis important. At least certain methods or embodiments of the presentinvention can be used to modify polymeric textile fibers and/or fabrics,for example using a fluorinated compound, to make the polymeric textilefibers and/or fabrics permanently waterproof and/or stain resistant.

Furthermore, in accordance with at least selected embodiments of thepresent invention, functionalized component A-B can be used to reducethe surface energy of a polyolefin membrane used in the wall of certainfragrance container devices. Certain fragrance container devicesfunction through the controlled release of a fragrance material throughthe wall or walls of a fragrance container device. The fragrancecontainer device can typically consist of a polyolefin and is often madeof polyethylene. However, the release rate of the fragrance through thepolyolefin membrane wall of the fragrance container device can belimited by the non-porous nature of the polyolefin membrane.Consequently, the fragrance container device must be made larger in sizeand/or the concentration of the fragrance in the fragrance containerdevice must be increased in order to achieve the desired release rate offragrance.

There is an economic need to use less fragrance in such fragrancecontainer devices while achieving the desired fragrance release rate.For this reason, use of a microporous polymeric membrane as the wallmaterial in a fragrance container device or container would facilitatethe movement of fragrance through the membrane wall of the fragrancecontainer device at a much more rapid rate. However, the use ofmicroporous polyolefin membranes in fragrance container deviceapplications has been limited by the tendency of the fragrance oils toleak through the membrane wall of the container. This disadvantage canbe overcome by using the present invention to modify the surface energyof the microporous membrane, for example, by using a fluorinatedfunctionalized polymer A-B to make the membrane or wall of the fragrancecontainer device oleophobic and resistant to leakage of the fragranceoils.

In accordance with at least selected embodiments of the presentinvention, the modified functionalized polymer A-B can modify a polymersubstrate which has a lower or higher surface energy that counteractsthe direct attachment of functional component A. More specifically,modified functionalized polymer A-B can covalently modify the polymersubstrate which has a polarity that limits and/or prevents the directattachment of functional polymer A. More specifically, the modifiedfunctionalized polymer A-B can modify the polymer substrate which has asurface that is hydrophilic or hydrophobic which can limit and/orprevent the direct attachment of functional component A. Still morespecifically, modified functionalized polymer A-B can modify the polymersubstrate which has a surface that is oleophilic or oleophobic which canlimit and/or prevent the attachment of functional component A.

At least certain embodiments of the present invention are directed tothe placement of a specific chemical functionality in modified polymer Awhich will enable functionalized polymer A to act as an adhesionpromoter or demoter to chemically react with the surface of a substrate.In accordance with at least selected possibly preferred embodiments, theinvention is directed to modifying functionalized polymer A with acarbene and/or nitrene intermediate which includes a crosslinking group.The incorporation of a crosslinking functional group enablesfunctionalized polymer component A to act as an adhesion promoter ordemoter polymer agent which can chemically modify the surface of asubstrate resulting in a durable or nonfugitive change to the surface ofthe substrate.

At least certain embodiments are directed to modifying certainfunctionalized polymers for the purpose of changing surface energy ofthe polymer substrate. This can lead to enhanced adhesion properties foradhesive or lamination applications, in particular, for cases in whichother adhesion promotion techniques could be detrimental to themechanical or chemical stability of the substrate.

At least certain embodiments are directed to modifying certainfunctionalized polymers with a single carbene and/or nitrene component Bor with a mixture of multifunctional carbene and/or nitrene component Bsfor the purpose of including biologically derived polymers and smallmolecules for end use applications that may require biological detectionor assaying. Proteins, DNA, RNA, naturally occurring polysaccharides, orother biologically relevant materials can be used for these types ofapplications.

Modifications of the surface of the polymer substrate can be made forthe purpose of changing its functionality. For example, a nominallychemically inert polymer substrate can be modified by decorating thesurface of the substrate with functional groups added by modifiedfunctional component A-B which is designed to participate in a secondarypost treatment reaction to modify a polymer substrate. Such a changealters the functionality of the polymer substrate for an intended enduse application. An example of such a post treatment reaction is atextile end use application in which the surface of a textile substratehas been reacted with modified component A-B so it can accept standardtextile dying chemical and procedures to generate substantiallydifferent end results.

The polymer substrate can consist of any synthetic or natural polymer orcopolymer such as olefinic, styrenic, silicone, urethane, acrylate,ester, vinyl, cellulosics, amides, aramids, ethers, orco-polymers,blends and/or mixtures of such. Additionally, the polymersubstrate can also be a cross linked network material, such asphenol-formaldehyde resin or rubber-type materials such as butadiene,isoprene, and neoprene. Additionally, the polymer substrate can be ahalogen-containing polymer such as Polytetrafluoroethylene (PTFE),Polyvinylidene fluoride (PVDF), Polyvinylidene Dichloride (PVDC), andPolyvinyl chloride (PVC).

The chemical structure of functional polymer A contains the desiredsurface functional group required by the polymer substrate in the enduse application. Functional polymer A can consist of similar polymers asthe polymer substrate. In addition, functional polymer A can consist ofpolyamines, polyols, polyamides, and blends, mixtures or co-polymers ofsuch.

In accordance with at least selected preferred embodiments, theinvention is directed to using as Component B a multifunctional material(f>2.0) that has pendant functional groups tailored to generate carbeneand/or nitrene species in situ. Component A and component B arechemically reacted to produce the active chemical species which canreact with the surface of the polymer substrate enabling the modifiedpolymer substrate to be useful in the intended end use application.

The ratio between component A and component B can be varied to generateoptimal performance properties in the end use application. Typicalcomponent A/component B application ratios could range from about 1.0 to200.0, depending on desired surface properties, intended end useapplication of the polymer substrate, and the reactivity of component Awith component B.

At least certain embodiments are directed to modifying certainfunctionalized polymers for the purpose of including biologicallyderived polymers and small molecules for applications that may requirebiological detection or assaying. Proteins, DNA, RNA, naturallyoccurring polysaccharides, or other biologically relevant materials canbe used for these types of applications.

At least certain embodiments are directed to modifying the surface of apolymer substrate with a mixture of multifunctional carbene and/ornitrene precursor component B which has been reacted with a desiredcomponent A functional synthetic polymer, small molecule, orbiologically active surface modifying agent.

Modifications of the surface of the polymer substrate can be made forthe purpose of changing its functionality. For example, a nominallychemically inert polymer substrate can be modified by decorating thesurface of the substrate with functional groups added by functionalcomponent A or indirectly by modifying the ‘component A-modified polymersubstrate’ in a secondary post treatment reaction. Such a change altersthe functionality of the polymer substrate for an intended end useapplication. An example of such a post treatment reaction is a textileend use application in which the surface of a textile substrate has beenreacted with modified component A-B so it can accept standard textiledying chemical and procedures to generate substantially different endresults.

At least selected embodiments of the present invention are directed tomodified porous membranes, methods of making modified porous membranes,and methods of using modified porous membranes. More particularly, theinvention is directed to chemically modified polyolefin microporousmembranes, methods of making chemically modified polyolefin microporousmembranes, and methods of using chemically modified polyolefinmicroporous membranes. Still more particularly, the invention isdirected to chemically modified polyolefin microporous batteryseparators or battery separator membranes, methods of making chemicallymodified polyolefin microporous battery separators or battery separatormembranes, and methods of using chemically modified polyolefinmicroporous battery separators or battery separator membranes.

In accordance with at least selected preferred embodiments, theinvention is directed to chemical modification of polyolefin microporousbattery separators or separator membranes by the chemical reaction ofcarbene and/or nitrene intermediates with the carbon-hydrogen bonds ofthe polyolefin, methods of improving the hydrophilicity or wettabilityof the polyolefin microporous battery separators or separator membranesin lithium-ion rechargeable batteries, methods of introducingcrosslinking into the polyolefin microporous battery separators orseparator membranes, and/or the like.

In accordance with at least selected preferred embodiments of theinvention, chemical modification of at least a portion of the surface ofpolyolefin microporous separators or separator membranes can beaccomplished by the chemical reaction of carbene and/or nitreneintermediates with the carbon-hydrogen bonds of the polyolefin. Thischemical reaction or treatment based on carbene and/or nitreneintermediates provides a method of more permanently improving thewettability of polyolefin microporous separators in lithium-ionrechargeable batteries. In addition, the preferred reaction of carbeneand/or nitrene intermediates with the C—C and C—H bonds in at least asurface layer of polyolefin microporous separator membranes can be usedto introduce crosslinking into the polyolefin which can improve the hightemperature stability of the polyolefin microporous separators ormembranes.

An exemplary battery separator may be a single layer, multiple layer ormultiple-ply battery separator made of one or more layers or plies ofpolyolefin porous membrane or film. The microporous membrane may be asymmetric membrane or an asymmetric membrane. The membrane may be madefrom one or more polyolefin polymers or blends including, but notlimited to, polyethylene (PE, including LDPE, LLDPE, and HDPE), ultrahigh molecular weight polyethylene (UHMWPE), polypropylene (PP),polymethylpentene (PMP), copolymers of any of the foregoing, andmixtures thereof. The membrane may be made by any suitable processincluding, but not limited to, a dry stretch process (also known as theCELGARD process) or a solvent process (also known as the gel extrusionor phase separation or extraction or wet process) or a netting (oraperture) process (the film is cast onto a chilled roll, the roll has apattern that is embossed onto the film, subsequently the embossed filmis stretched (MD/TD), whereby large pores are formed along the embossedpattern). The membrane preferably has the necessary characteristics tooperate as a battery separator in a battery such as a lithium battery,more preferably a rechargeable lithium-ion battery, or the like. Thechemically modified membrane of the present invention may be the outerlayer of a tri-layer membrane (e.g., PP/PE/PP or PE/PP/PE) or othermulti-layer membrane or separator such as a tri-layer shutdownseparator.

Polyolefins are a class or group of thermoplastic polymers derived fromsimple olefins. Polyolefins generally include polyethylene,polypropylene, polybutylene, polymethyl pentene, and copolymers thereof.Polyolefin articles generally include fibers and films, but also includemicroporous films and microporous hollow fibers. Microporous refers toan article which has a plurality of pores with effective diameters of 1micron or less. Hydrophobic polyolefins refer to polyolefins havingsurface energies equivalent to or less than the surface energy ofpolyethylene.

In accordance with at least certain embodiments, a polyolefin article ismade more hydrophilic or wettable by chemical modification of at least aportion of the surface of the polyolefin article, such as a microporousseparator or membrane by the chemical reaction of carbene and/or nitreneintermediates with the carbon-hydrogen bonds of the polyolefin. Inaddition, the preferred reaction of carbene and/or nitrene intermediateswith the C—C and C—H bonds in at least a surface layer of the polyolefinarticle can be used to introduce crosslinking into the polyolefin whichcan improve the high temperature stability, the strength, and/or thelike. The foregoing hydrophilic polyolefin articles may be used in anyapplication where a hydrophilic polyolefin is necessary or desirable,for example, air filtration, air cleaning, water filtration, watercleaning, water purification, medical equipment, separation equipment,semiconductor manufacture, battery cell separator, ultrafiltrationequipment, and the like.

With regard to battery or cell separators, the chemical treatment isapplied to one or preferably both surfaces of the microporous polyolefinmembrane. This treated separator is particularly suitable forlithium-ion secondary batteries.

With regard to the separation, filtration, cleaning, and purificationequipment, particularly where microporous polyolefin hollow fibers orflat sheet membranes are used, higher flux rates are obtainable by useof the modified materials.

The microporous membrane is typically a hydrophobic, polyolefin polymer.Such polymers include, for example, polyethylene, polypropylene, andblends, mixtures or co-polymers thereof. The method of manufacturing themembrane is not critical, and may include, for example, the “dry”stretch (or Celgard) process or the “solvent” stretch (or phaseinversion) process. Such membranes may have a thickness of about 75microns or less. For cetain applications, dry process polypropylenemembranes may be preferred.

Chemical modification of carbon-hydrogen and other bonds in polyolefinsas a means to permanently modify the hydrophobic nature of polyolefinscan be challenging due to the limited number of available chemicalreactions. The carbon-hydrogen and carbon-carbon bonds are both verystable making it difficult to permanently modify polyolefins such aspolypropylene and polyethylene. Polyolefins such as polypropylene andpolyethylene are commonly used in microporous separator membranes inlithium-ion rechargeable batteries. An important performance property ofpolyolefin microporous separator membranes is easy wettability by thenon-aqueous electrolyte solvents typically used in lithium-ionrechargeable batteries. Currently, various surfactants are applied as acoating to alter the hydrophobic nature of the polyolefin microporousseparator membrane and increase its wettability by non-aqueouselectrolyte solvents. Certain surfactant coatings may only providetemporary wettability since they are only physically adsorbed to thesurface of the polyolefin microporous separator membrane.

In accordance with the present invention, a more permanent solution toproviding wettability may utilize a chemical reaction to covalentlyattach surface modifying agents to the polyolefin microporous separatormembrane. One of the few reactions that can react with carbon-hydrogen(C—H) bonds in polyolefins involves the use of carbene and/or nitreneintermediates. Carbene and nitrene intermediates are reactiveintermediates of carbon and nitrogen, respectively, which have theability to insert themselves into C—H bonds of a polyolefin either withor without the presence of a transition metal catalyst. FIG. 1 depictsthe respective formation of carbene and nitrene intermediates from heator light.

Transition metal catalysts are typically expensive, and should bereadily recovered to make an economical process. There are someprecursors that can provide carbene intermediates through heat, light,or through chemical reaction.

Carbene intermediates can be formed through thermolysis or photolysis ofdiazo compounds. A chemical reaction between a strong base and acompound prone to α-elimination (such as Methylene Chloride, Chloroform,Bromoform, etc.) can also produce carbene intermediates. Nitrenes aretypically formed through thermo- or photolysis of azides (of particularimportance are aryl azides and sulfonyl azides) and through thethermolysis of isocyanates. Thermal decomposition may tend to have moreefficient insertion than other generation methods.

Once the reactive intermediate is formed, its lifetime is typically veryshort. When introduced to the surface of the polyolefin separatormembrane in an appropriate timeframe, an insertion reaction such as thatshown in FIG. 1 can occur. A polyolefin with a new functionalityinserted into a C—H bond can be achieved through radical abstraction andrecombination or through a concerted reaction. The surface properties ofthe polyolefin can be modified by the selection of the R and R′functional groups in the carbene and/or nitrene intermediate.

For example, if a diazo material is created with a long poly(ethylenegycol) tail, the resulting surface modification would demonstrateenhanced hydrophilicity, leading to enhanced wetting properties of thepolyolefin separator membrane by very polar materials.

Producing a variety of hydrophilic molecules is not limited to onlyethylene glycol oligomers and polymers. Further modifications couldinclude hydroxyethyl acrylate, methacrylates, polyethyleneimines,modified celluloses or chitosan. These can be in oligomeric or polymericform.

Carbene and/or nitrene surface treatment could also be accomplished witha wide variety of small molecule functional groups. Carboxylic acids,alcohols, thiols, amines (primary, secondary, tertiary, and quaternary),guanidinium, ethers, esters, and carbonates are functional groups thatcan produce some hydrophilic nature to a polyolefin microporousseparator membrane.

A significant increase in the wettability of polypropylene microporousseparator membranes by very polar electrolytes can be achieved throughthe present chemical modifications of the polypropylene microporousseparator membrane allowing a broader range of current and futureelectrolytes that can be used in lithium-ion rechargeable batteries.

For example, the wetting properties of the substrate can be drasticallymodified based on the substitutions to the molecular additive. Perfluorogroups could impart superhydrophobic behavior, while polyethyleneglycol) additions can increase water wettability. Poly(dimethylsiloxane)can be used to enhance the feel of the material by making the substratemore pleasant to the touch. Furthermore, surface or bulk crosslinking ofthe material with a multifunctional carbine and/or nitrene precursor andtreatment can lead to enhanced cross-web toughness.

Carbene and/or nitrene intermediates involving a plurality of chemicalreactions can also be used to insert a specific structure designed toinduce crosslinking in a polyolefin microporous separator membrane.Since crosslinks in polyolefin materials will anchor polymer moleculestogether, an additional advantage is gained that enhances battery safetythrough the reinforcement of cross-web strength of the microporouspolyolefin separator membrane.

As an example, a molecule incorporating greater than 1 carbene and/ornitrene precursor can be applied to the polyolefin microporous separatormembrane after the pores have been formed, creating a crosslinkedsurface. Crosslinking of the polyolefin microporous separator membranesurface can be important in high temperature end use applications. Bycreating a lightly crosslinked surface, the temperature resulting inloss of the structural integrity of the polyolefin microporous separatormembrane can be increased and tailored to a particular temperature rangebased on the crosslink density. This can be accomplished as thecrosslinked material can retain the molten bulk material that has nocrosslinks. As the density of surface crosslink is increased, theability to act as an exoskeleton which maintains structural integrity ofthe polyolefin microporous separator membrane is increased.

In addition, the crosslinking molecule incorporating greater than 1carbene and/or nitrene precursor can be added to a polyolefin polymerresin during the extrusion process to form a nonporous precursorseparator membrane. This precursor is then stretched to form the poresof the microporous polyolefin membrane resulting in a microporouspolyolefin membrane with improved tensile strength and melt integrity athigh temperatures.

In at least selected embodiments, the separator may be a nonwovenmaterial such as a nonwoven made up of fibers and chemically modified toimprove the high temperature melt integrity of the nonwoven and/or toimprove the wettability of the nonwoven.

In accordance with at least certain objects of the instant invention,there are provided new, improved or modified surface modified polymericmaterials, modified functionalized polymers, functional polymers,chemically modified substrates including modified functionalizedpolymers, methods of making and/or using surface modified polymericmaterials, modified functionalized polymers, functional polymers, and/orchemically modified substrates including modified functionalizedpolymers, methods of modifying a functionalized polymer and/or methodsof using modified functionalized polymers to chemically react with thesurface of a substrate, and/or methods of using such chemically modifiedsubstrates. At least certain embodiments or objects are directed tomodified functionalized polymers, functional polymers, and methods ofmodifying functionalized polymers for chemically modifying porous and/ornonporous polymer substrates and/or methods of using such modifiedsubstrates. At least selected embodiments or objects are directed tomodified functionalized polymers, functional polymers, and methods ofmodifying functionalized polymers for chemically modifying porous and/ormicroporous polymer substrates and methods of using such modifiedsubstrates. At least certain embodiments or objects are directed tomodifying certain functionalized polymers to enable them to effect achange in the surface property of a substrate. In accordance with atleast selected possibly preferred embodiments, the invention is directedto using a carbene and/or nitrene crosslinking modifier to chemicallymodify a functionalized polymer to form a modified functionalizedpolymer which can chemically modify the surface of a substrate andeffect a change in the surface properties of the substrate for anintended application. In accordance with at least selected possiblypreferred embodiments, the invention is directed to using a carbeneand/or nitrene crosslinking modifier (component B) to covalently modifya polymeric surface with a functionalized polymer (component A). Such amodification may alter the chemical reactivity of the polymeric surfaceenabling the modified substrate to have a specifically designedfunctionality for an intended end use or application.

With reference to FIG. 1, nitrene generation, carbene generation, andthe insertion mechanism in accordance with at least selected possiblypreferred embodiments of the present invention are shown. The R, R′and/or R/R′ groups may be modified to tailor surface characteristics ofa polyolefin, such as the surface of a polyolefin substrate, forexample, the R/R′ groups can be modified to tailor surfacecharacteristics such as wetting.

With reference to FIG. 2, a surface modified polymeric material or achemically modified substrate including modified functionalized polymersin accordance with at least selected possibly preferred embodiments ofthe present invention is shown.

With reference to FIG. 3, a coated or treated surface modified polymericmaterial or a coated or treated chemically modified substrate, forexample, modified by modified functionalized polymers to facilitate thedesired coating or treatment (such as by raising or lowering the surfaceenergy of the polymeric material or substrate suface) in accordance withat least selected possibly preferred embodiments of the presentinvention is shown.

The present invention relates to new, improved or modified polymermaterials, membranes, substrates, and the like and to new, improved ormodified methods for permanently modifying the physical and/or chemicalnature of surfaces of the polymer substrate for a variety of end uses orapplications. For example, one improved method uses a carbene and/ornitrene modifier to chemically modify a functionalized polymer to form achemical species which can chemically react with the surface of apolymer substrate and alter its chemical reactivity. Such method mayinvolve an insertion mechanism to modify the polymer substrate toincrease or decrease its surface energy, polarity, hydrophilicity orhydrophobicity, oleophilicity or oleophobicity, and/or the like in orderto improve the compatibility of the polymer substrate with, for example,coatings, materials, adjoining layers, and/or the like. Furthermore,this invention can be used to produce chemically modified membranes,fibers, hollow fibers, textiles, and the like, for example, to producepolyolefin microporous battery separators or membranes having improvedhydrophilicity or wettability, having crosslinking in at least thesurface of the polyolefin which can improve the high temperaturestability, and/or the like.

In accordance with at least selected oleophobic related embodiments:

1. The polymer surface (film, fiber,or bulk material) is modified with amixture of multifunctional carbene and/or nitrene precursor (componentB) and a desired functional synthetic polymer (component A)

-   -   a. The polymer surface can be any synthetic or natural polymer        or copolymer from the following polymer classes: olefinic,        styrenic, silicone, urethane, acrylate, ester, vinyl,        cellulosics, amides, aramids, ethers and the like. It can also        be a cross linked network material, such as phenol-formaldehyde        resin or rubber type materials like butadiene, isoprene, and        neoprene. Additionally, modifications to other halogen        containing polymers like PTFE, PVDF, PVDC, and PVC can be        effected.    -   b. Component A is a material typically found in hydrophobic or        oleophobic treatment applications. Materials like fluorinated        acrylic copolymer systems heavily used as textile treatments or        chitin based materials may provide suitable resistance to oils.        Additionally, component A may be a composite material with        additional nanoparticles to generate nanoscale roughness for        resistance enhancement.    -   c. Component B is a multifunctional material (f>2.0) that has        pendant functional groups tailored to generate carbene and/or        nitrene species in situ.

2. The coating weight for these can come from an organic or aqueoussolution and developed by heat treatment or exposure to UV light.

-   -   a. The modification can be added to a surface in enough quantity        to effect the surface properties that are required for the        intended application. Typical application rates may range from        about 0.05 g/m2 to 1.0 g/m2 or more, and is dependent on        substrate surface area, solution viscosity, cure rate, amongst        other factors.    -   b. The ratio between component A and B can be variable to        generate the best properties. Typical A/B application weight        ratio might range from about 0.5 to 200.0 or more, depending on        desired surface properties and the reactivity of A with B.

In accordance with at least selected objects or embodiments, theinvention provides or is directed to:

-   -   Modified polymer substrates, surface modified polymeric        materials, modified functionalized polymers, functional        polymers, or chemically modified substrates including modified        functionalized polymers as shown or described herein.

The above invention, wherein the modified polymer substrate is achemically modified polymer substrate.

The above invention, wherein the modified polymer substrate is at leastone of a porous polymer substrate, a nonporous polymer substrate, aporous hollow fiber, a nonporous hollow fiber, a porous batteryseparator or membrane, a film, a chemically modified polymer substrate,a fiber, a textile, a polyolefin material, a polyolefin blend, apolypropylene material, a polyethylene material, a polymer surfacelayer, a composite, a combination thereof, or the like.

The above invention, wherein the modified polymer substrate ischemically modified by the chemical reaction of at least one of carbeneand nitrene intermediates with the carbon-hydrogen bonds of the polymersubstrate to covalently attach at least one modified functionalizedpolymer thereto.

Methods of making or methods of using modified polymer substrates,surface modified polymeric materials, modified functionalized polymers,functional polymers, or chemically modified substrates includingmodified functionalized polymers, films, hollow fibers, fibers,textiles, composites, layers, surfaces, chemically modified polyolefinmicroporous membranes, chemically modified polyolefin microporousbattery separators or battery separator membranes, microporous batteryseparators or battery separator membranes, ribbed materials,combinations thereof, methods of improving the wettability of thepolyolefin microporous battery separators in lithium ion rechargeablebatteries, methods of introducing crosslinking into the polyolefinmicroporous separators, and/or the like as shown or described herein.

The above method including at least one step of chemically modifying apolyolefin microporous battery separator membrane by the chemicalreaction of at least one of carbene and nitrene intermediates with thecarbon-hydrogen bonds of the polyolefin, improving the wettability of apolyolefin microporous battery separator adapted for use in alithium-ion rechargeable battery, introducing crosslinking into apolyolefin microporous battery separator, and/or the like.

In a battery separator, the improvement comprising a polyolefinmicroporous membrane having at least a portion of at least one surfacechemically modified.

The above separator, wherein said chemically modified polyolefin has asurface energy of equal to or greater than the surface energy ofpolyethylene.

The above separator, wherein said chemical modification raises thesurface energy of the polyolefin to at least about 48 dynes/cm.

The above separator, wherein the polyolefin microporous membrane ischemically modified to raise the surface energy of said membrane.

The above separator, wherein said polyolefin is selected from the groupconsisting of polyethylene, polypropylene, blends, mixtures, andcopolymers thereof.

In a battery comprising an anode, a cathode, an electrolyte, and aseparator, the improvement comprising the above separator.

In a textile comprising a polyolefin microporous membrane, theimprovement comprising said polyolefin microporous membrane having atleast a portion of at least one surface chemically modified.

The above textile, wherein said chemically modified polyolefin membranehas a surface modification comprising a cellulosic material for thepurpose of a secondary standard textile treatment, such as dyeing orother finishing step.

The above textile, wherein said chemically modified polyolefin membranehas a surface energy of equal to or less than the surface energy ofpolytetrafluoroethylene.

The above textile, wherein said chemical modification lowers the surfaceenergy of the polyolefin membrane to at most about 20 dynes/cm.

A textile laminate containing at least one synthetic or natural fabricbonded with the above polyolefin membrane.

An oleophobic modified polyolefin textile membrane comprising apolyolefin microporous membrane chemically modified to lower the surfaceenergy of said membrane, wherein said polyolefin is selected from thegroup consisting of polyethylene, polypropylene, and copolymers thereof,and wherein said chemically modified polyolefin has a surfacemodification consisiting of an oleophobic polymer or combination ofpolymers, and/or the like.

A microporous polymer membrane having at least one surface or portionchemically modified by the chemical reaction of at least one of carbeneand nitrene intermediates to covalently attach at least one modifiedfunctionalized polymer thereto to provide a durable chemicalmodification that provides at least one of improved wettability, reducedwettability, hydrophilicity, hydrophobicity, oleophobicity, resistanceto fouling by biological materials, resistance to wetting by organicsolvents, resistance to wetting by methanol, ethanol, 1-propanol,acetone, and other polar type solvents, resistance to wetting byaliphatic and aromatic type solvents.

Potentially preferred porous membranes (porous polymer substrates) aredisclosed in US Published Patent Applications 2007/0196638 A1 publishedAug. 23, 2007 and 2011/0223486 A1 published Sep. 15, 2011, both herebyincorporated by reference herein. Potentially preferred component Bmaterials such as carbine precursors are disclosed in WO PublishedPatent Applications 2010/100410 A1 published Sep. 10, 2010 and2010/100413 A2 published Sep. 10, 2010, both hereby incorporated byreference herein. Potentially preferred component A materials such asfluorocopolymers are disclosed in US Published Patent Application2012/0070648 A1 published Mar. 22, 2012, which is hereby incorporated byreference herein.

Many other modifications and variations of the present invention arepossible to the skilled practitioner in the field in light of theteachings herein. It is therefore understood that, within the scope ofthe claims, the present invention can be practiced other than as hereinspecifically described.

1. Modified polymer substrates, surface modified polymeric materials,modified functionalized polymers, functional polymers, or chemicallymodified substrates including modified functionalized polymers as shownor described herein.
 2. The invention of claim 1, wherein the modifiedpolymer substrate is a chemically modified polymer substrate.
 3. Theinvention of claim 1, wherein the modified polymer substrate is at leastone of a porous polymer substrate, a nonporous polymer substrate, aporous hollow fiber, a nonporous hollow fiber, a porous batteryseparator or membrane, a film, a chemically modified polymer substrate,a fiber, a textile, a polyolefin material, a polyolefin blend, apolypropylene material, a polyethylene material, a polymer surfacelayer, a composite, a combination thereof, or the like.
 4. The inventionof claim 1, wherein the modified polymer substrate is chemicallymodified by the chemical reaction of at least one of carbene and nitreneintermediates with the carbon-hydrogen bonds of the polymer substrate tocovalently attach at least one modified functionalized polymer theretovia an insertion mechanism.
 5. Methods of making or methods of usingmodified polymer substrates, surface modified polymeric materials,modified functionalized polymers, functional polymers, or chemicallymodified substrates including modified functionalized polymers, films,hollow fibers, fibers, textiles, composites, layers, surfaces,chemically modified polyolefin microporous membranes, chemicallymodified polyolefin microporous battery separators or battery separatormembranes, microporous battery separators or battery separatormembranes, ribbed materials, combinations thereof, methods of improvingthe wettability of the polyolefin microporous battery separators inlithium-ion rechargeable batteries, methods of introducing crosslinkinginto the polyolefin microporous separators, and/or the like as shown ordescribed herein.
 6. The method of claim 5 including at least one stepof chemically modifying a polyolefin microporous battery separatormembrane by the chemical reaction of at least one of carbene and nitreneintermediates with the carbon-hydrogen bonds of the polyolefin,improving the wettability of a polyolefin microporous battery separatoradapted for use in a lithium ion rechargeable battery, introducingcrosslinking into a polyolefin microporous battery separator, and/or thelike.
 7. In a battery separator, the improvement comprising a polyolefinmicroporous membrane having at least a portion of at least one surfacechemically modified.
 8. The separator of claim 7, wherein saidchemically modified polyolefin has a surface energy of equal to orgreater than the surface energy of polyethylene.
 9. The separator ofclaim 7, wherein said chemical modification raises the surface energy ofthe polyolefin to at least about 48 dynes/cm.
 10. The separator of claim7, wherein the polyolefin microporous membrane is chemically modified toraise the surface energy of said membrane.
 11. The separator of claim 7,wherein said polyolefin is selected from the group consisting ofpolyethylene, polypropylene, blends, mixtures, and copolymers thereof.12. In a battery comprising an anode, a cathode, an electrolyte, and aseparator, the improvement comprising the separator according to claim7.
 13. In a textile comprising a polyolefin microporous membrane, theimprovement comprising said polyolefin microporous membrane having atleast a portion of at least one surface chemically modified.
 14. Thetextile of claim 13, wherein said chemically modified polyolefinmembrane has a surface modification comprising a cellulosic material forthe purpose of a secondary standard textile treatment, such as dyeing orother finishing step.
 15. The textile of claim 13, wherein saidchemically modified polyolefin membrane has a surface energy of equal toor less than the surface energy of polytetrafluoroethylene.
 16. Thetextile of claim 13, wherein said chemical modification lowers thesurface energy of the polyolefin membrane to at most about 20 dynes/cm.17. A textile laminate containing at least one synthetic or naturalfabric bonded with the polyolefin membrane of claim
 13. 18. Anoleophobic modified polyolefin textile membrane comprising a polyolefinmicroporous membrane chemically modified to lower the surface energy ofsaid membrane, wherein said polyolefin is selected from the groupconsisting of polyethylene, polypropylene, and copolymers thereof, andwherein said chemically modified polyolefin has a surface modificationconsisiting of an oleophobic polymer or combination of polymers, and/orthe like.
 19. A microporous polymer membrane having at least one surfaceor portion chemically modified by the chemical reaction of at least oneof carbene and nitrene intermediates to covalently attach at least onemodified functionalized polymer thereto to provide a durable chemicalmodification that provides at least one of improved wettability, reducedwettability, hydrophilicity, hydrophobicity, oleophobicity, resistanceto fouling by biological materials, resistance to wetting by organicsolvents, resistance to wetting by methanol, ethanol, 1-propanol,acetone, and other polar type solvents, and/or resistance to wetting byaliphatic and aromatic type solvents.